WO2023117198A1 - Membrane pour utilisation avec des milieux contenant de l'hydrogène, et transducteur comprenant une telle membrane - Google Patents

Membrane pour utilisation avec des milieux contenant de l'hydrogène, et transducteur comprenant une telle membrane Download PDF

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Publication number
WO2023117198A1
WO2023117198A1 PCT/EP2022/081288 EP2022081288W WO2023117198A1 WO 2023117198 A1 WO2023117198 A1 WO 2023117198A1 EP 2022081288 W EP2022081288 W EP 2022081288W WO 2023117198 A1 WO2023117198 A1 WO 2023117198A1
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WIPO (PCT)
Prior art keywords
coating
membrane
space
fluid medium
hydrogen
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PCT/EP2022/081288
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German (de)
English (en)
Inventor
Giovanni Mastrogiacomo
Hans Beat MÄRKI
Thomas Cadonau
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Kistler Holding Ag
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Publication of WO2023117198A1 publication Critical patent/WO2023117198A1/fr

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Classifications

    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01L—MEASURING FORCE, STRESS, TORQUE, WORK, MECHANICAL POWER, MECHANICAL EFFICIENCY, OR FLUID PRESSURE
    • G01L9/00—Measuring steady of quasi-steady pressure of fluid or fluent solid material by electric or magnetic pressure-sensitive elements; Transmitting or indicating the displacement of mechanical pressure-sensitive elements, used to measure the steady or quasi-steady pressure of a fluid or fluent solid material, by electric or magnetic means
    • G01L9/0041—Transmitting or indicating the displacement of flexible diaphragms
    • G01L9/0051—Transmitting or indicating the displacement of flexible diaphragms using variations in ohmic resistance
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01L—MEASURING FORCE, STRESS, TORQUE, WORK, MECHANICAL POWER, MECHANICAL EFFICIENCY, OR FLUID PRESSURE
    • G01L9/00—Measuring steady of quasi-steady pressure of fluid or fluent solid material by electric or magnetic pressure-sensitive elements; Transmitting or indicating the displacement of mechanical pressure-sensitive elements, used to measure the steady or quasi-steady pressure of a fluid or fluent solid material, by electric or magnetic means
    • G01L9/0041—Transmitting or indicating the displacement of flexible diaphragms
    • G01L9/008—Transmitting or indicating the displacement of flexible diaphragms using piezoelectric devices
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01L—MEASURING FORCE, STRESS, TORQUE, WORK, MECHANICAL POWER, MECHANICAL EFFICIENCY, OR FLUID PRESSURE
    • G01L19/00—Details of, or accessories for, apparatus for measuring steady or quasi-steady pressure of a fluent medium insofar as such details or accessories are not special to particular types of pressure gauges
    • G01L19/06—Means for preventing overload or deleterious influence of the measured medium on the measuring device or vice versa
    • G01L19/0627—Protection against aggressive medium in general
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01L—MEASURING FORCE, STRESS, TORQUE, WORK, MECHANICAL POWER, MECHANICAL EFFICIENCY, OR FLUID PRESSURE
    • G01L19/00—Details of, or accessories for, apparatus for measuring steady or quasi-steady pressure of a fluent medium insofar as such details or accessories are not special to particular types of pressure gauges
    • G01L19/06—Means for preventing overload or deleterious influence of the measured medium on the measuring device or vice versa
    • G01L19/0627—Protection against aggressive medium in general
    • G01L19/0645—Protection against aggressive medium in general using isolation membranes, specially adapted for protection
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01L—MEASURING FORCE, STRESS, TORQUE, WORK, MECHANICAL POWER, MECHANICAL EFFICIENCY, OR FLUID PRESSURE
    • G01L19/00—Details of, or accessories for, apparatus for measuring steady or quasi-steady pressure of a fluent medium insofar as such details or accessories are not special to particular types of pressure gauges
    • G01L19/06—Means for preventing overload or deleterious influence of the measured medium on the measuring device or vice versa
    • G01L19/0672—Leakage or rupture protection or detection
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01L—MEASURING FORCE, STRESS, TORQUE, WORK, MECHANICAL POWER, MECHANICAL EFFICIENCY, OR FLUID PRESSURE
    • G01L19/00—Details of, or accessories for, apparatus for measuring steady or quasi-steady pressure of a fluent medium insofar as such details or accessories are not special to particular types of pressure gauges
    • G01L19/14—Housings
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01L—MEASURING FORCE, STRESS, TORQUE, WORK, MECHANICAL POWER, MECHANICAL EFFICIENCY, OR FLUID PRESSURE
    • G01L7/00—Measuring the steady or quasi-steady pressure of a fluid or a fluent solid material by mechanical or fluid pressure-sensitive elements
    • G01L7/02—Measuring the steady or quasi-steady pressure of a fluid or a fluent solid material by mechanical or fluid pressure-sensitive elements in the form of elastically-deformable gauges
    • G01L7/08—Measuring the steady or quasi-steady pressure of a fluid or a fluent solid material by mechanical or fluid pressure-sensitive elements in the form of elastically-deformable gauges of the flexible-diaphragm type
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01L—MEASURING FORCE, STRESS, TORQUE, WORK, MECHANICAL POWER, MECHANICAL EFFICIENCY, OR FLUID PRESSURE
    • G01L9/00—Measuring steady of quasi-steady pressure of fluid or fluent solid material by electric or magnetic pressure-sensitive elements; Transmitting or indicating the displacement of mechanical pressure-sensitive elements, used to measure the steady or quasi-steady pressure of a fluid or fluent solid material, by electric or magnetic means
    • G01L9/0041—Transmitting or indicating the displacement of flexible diaphragms
    • G01L9/0072—Transmitting or indicating the displacement of flexible diaphragms using variations in capacitance

Definitions

  • Membrane for use with fluid media containing hydrogen and sensor comprising such a membrane
  • the invention relates to a membrane for use with hydrogen-containing fluid media and a sensor comprising such a membrane.
  • a membrane separates a fluid medium in a first space from a second space.
  • sensors often have a diaphragm.
  • the membrane separates a measuring arrangement, for example a pickup element, from the fluid medium whose pressure is to be determined.
  • a fluid medium is a gaseous and/or liquid medium.
  • a membrane usually has a surface with a first extent and a second extent, which first extent and second extent are formed largely perpendicularly to a longitudinal axis. In a third extension parallel to the longitudinal axis, the membrane has a thickness, also called wall thickness.
  • a fluid medium is understood below to mean a hydrogen-containing fluid medium which has at least 1% by volume (percent by volume) of hydrogen.
  • the surface of the membrane usually has an area which is in contact with the fluid medium in a first space.
  • a pressure sensor the pressure of the fluid medium acting on the area of the membrane is passed on to a pressure sensor element, or sensor element for short, with as little loss as possible. So that the sensitivity
  • the area of the membrane that is directly exposed to the fluid medium must have the highest possible resilience or the lowest possible rigidity.
  • the material in this area with low rigidity must not be irreversibly deformed by the measurement pressure. If materials with a yield point of around 400 MPa (megapascals) are used, the membrane must be made thick enough so that it is not irreversibly deformed.
  • the membrane can also have thicker areas, with which the membrane is connected to a sensor housing, for example. The thicker areas can also serve to improve the stability of the membrane.
  • the yield strength of a metallic material is determined by the standard DIN EN ISO 6892-1. It corresponds to the R P 0.2 • value.
  • the surface of a membrane may extend substantially along the first dimension and the second dimension, but may be partially curved toward the longitudinal axis.
  • Diaphragms can also separate a fluid medium from other types of sensing elements, for example temperature transducers in which a temperature sensing element is separated from the fluid medium by a diaphragm.
  • the temperature of the fluid medium is passed on to a temperature sensor element through the membrane.
  • the membrane should be as thin-walled as possible so that the heat transfer coefficient is as large as possible.
  • Corrosion is generally understood to mean a measurable change in a material. Corrosion can occur from exposure to a variety of substances. Corrosion of metallic materials in connection with various alkalis or acids, gases such as hydrogen or oxygen, salt water and many other substances is well known.
  • corrosion refers to corrosion by atomic and/or molecular hydrogen.
  • the membrane must be both tight and resistant to atomic and/or molecular hydrogen. Therefore, for membranes that are also heat-resistant above 200°C, commercially available, hydrogen-resistant and polycrystalline metals, such as the austenitic steel 1.4404 (also known as 316 L) with a yield strength of around 400 MPa at room temperature or the nickel-based alloy 2.4819 (also known as C-276) with a yield strength of also around 400 MPa at room temperature is used. However, these materials are characterized by an average grain size of more than 20 ⁇ m.
  • Coarse-grained, polycrystalline metals are less suitable as materials for thin membranes with a thickness of less than 500 ⁇ m, since the material could not behave isotropically due to the few crystal grains in the thin-walled area of the membranes.
  • the diffusion path for molecular and/or atomic hydrogen along the grain boundaries between the crystal grains through coarse-grained areas is relatively short. This is disadvantageous since hydrogen could easily diffuse through the membrane over a short distance.
  • the designation 1.4404 as well as other material numbers mentioned below correspond to DIN EN 10027-2.
  • Hydrogen embrittlement is understood as meaning a change in the ductility and strength of a metal or metal alloy as a result of the penetration and subsequent storage of hydrogen in the lattice structure of the metal or metal alloy. As a result, hydrogen-induced cracking can occur, which limits the use of vulnerable materials in hydrogen-contacting applications.
  • the materials steel 1.4404 also known as 316L
  • alloy 2.4819 also known as C-276 are generally considered to be corrosion-resistant. They have a low yield point and are therefore more plastically deformable than materials with a higher yield point, even when less force is applied.
  • membranes are often made thicker than 500 ⁇ m. However, this is disadvantageous due to the high inertial mass of a thick membrane. A thick membrane also has a higher rigidity.
  • pressure sensors have a space behind the membrane filled with a fluid pressure transmission medium. In this embodiment, the risk of irreversible plastic deformation of the membrane is lower, since the fluid pressure transmission medium counteracts deformation of the membrane.
  • the fluid pressure transmission medium for example a slightly compressible oil, transmits the pressure acting on the membrane to a measuring element spaced apart from the membrane.
  • the membrane must continue to transmit the pressure with as little loss as possible, ie the membrane should advantageously be made thin.
  • the fluid medium to be measured contains hydrogen, hydrogen accumulates in the fluid pressure transmission medium over time, as a result of which the volume increases and as a result the membrane bulges outwards.
  • the membrane is inflated by the hydrogen diffused through the membrane. On the one hand, this can damage the membrane and, on the other hand, it changes the pressure conditions around the measuring element.
  • a long-term stability of the sensor is negatively influenced by the diffusion of the molecular and/or atomic hydrogen through the membrane.
  • Document US20050109114A1 describes a sensor with a membrane made of alloy 2.4819 (also known as C-276). Although the material itself is regarded as corrosion-resistant, it is not impervious to hydrogen due to the thinness of the membrane. The diffusion of molecular and/or atomic hydrogen should be avoided by depositing a soft gold layer on the membrane.
  • the gold layer is largely chemically inert and thus reduces dissociation of molecular components of a fluid medium that is in contact with the membrane is. A dissociation of molecular components of a fluid medium or other chemical reactions on and with a surface can lead to corrosion of the surface.
  • the soft gold layer is not scratch-resistant and can accordingly be damaged during use and then no longer act as a diffusion barrier for hydrogen.
  • the object of the invention is to improve a membrane in such a way that the disadvantages mentioned are reduced. It is a further object of the invention to achieve improved corrosion resistance of the membrane to atomic and/or molecular hydrogen.
  • the invention relates to a membrane for hermetically separating a first space with a hydrogen-containing fluid medium from a second space.
  • the membrane has a metallic material.
  • the membrane has a coating to reduce the permeability with respect to molecular and/or atomic hydrogen, which coating at least in an area which is in contact with the fluid medium when used, between the metallic material of the membrane and the fluid medium is arranged.
  • the coating has oxides, carbides or nitrides, for example aluminum oxides, aluminum carbides, aluminum nitrides, chromium oxides, chromium nitrides, silicon oxides, silicon carbides, silicon nitrides, titanium oxides, titanium carbides, titanium nitrides, zirconium conium oxides, rare earth carbides or nitrides or rare earth oxides.
  • the coating has at least one non-stoichiometric oxide, carbide or nitride.
  • the coating preferably has a non-stoichiometric mixture.
  • the membrane is, for example, a membrane for a sensor for determining a pressure of the fluid medium.
  • a metallic material is preferably an alloy of chemical elements comprising at least one metal and at least one further chemical element.
  • the membrane is intended for separating a space with a hydrogen-containing fluid medium from another space.
  • a hydrogen-containing fluid medium has at least 1% by volume of hydrogen and is also referred to below as a corrosive or corrosive fluid medium.
  • the metallic material of the membrane is made of a metal or a metal alloy.
  • a metal or a metal alloy are, for example, nickel-based alloys such as electroformed nickel, nickel 270, nickel 301, K-Monel, or titanium-based alloys such as pure titanium, Ti-6Al-4V, Ti-5Al-2.5Sn , Ti-ll.5Mo-6Zr-4.5Sn, Alpha-2 TiAl alloy, Gamma-TiAl alloy, or copper based alloys such as OFHC copper, Aluminum Bronze, Be-Cu alloys, GRCop-84 (Cu-8Cr -4Nb), NARloy-Z (Cu-3Ag-0.5Zr), 70-30 Brass, or aluminum based alloys such as 1100-T0, 2011, 2024, 5086, 6061-T6, 6063, 7039, 7075-T73, or auste- nitic steels such as CG-27, Tenelon, A302B, A286, 216, 304L, 304N,
  • alloys are described in more detail in JA Lee, Hydrogen Embittlement, NASA/TM-2016-218602, Alabama, US (2016), Tables 2, 3 and 4.
  • the alloys are suitable as a metallic material for the production of a membrane, with different dimensions of the membrane being selected depending on the material properties.
  • some alloys are only conditionally suitable for direct exposure to a fluid medium containing hydrogen.
  • the coating of the metallic material gives the person skilled in the art the opportunity to test the metallic material of the membrane according to suitable physical properties such as rigidity, thermal conductivity, coefficient of thermal expansion or select yield point.
  • the coating protects the metallic material against corrosion caused by hydrogen. Hydrogen resistance of the metallic material is advantageous but not necessary.
  • Some of the aforementioned metallic materials have coarse-grained, polycrystalline structures, which are less suitable as materials for thin membranes with a thickness of less than 500 microns, as described above, in direct contact with a hydrogen-containing fluid medium.
  • coating the membrane eliminates this disadvantage and thus allows a relatively large selection of materials for use as the metallic material of the membrane.
  • the membrane at least partially has a thickness of less than 500 ⁇ m.
  • a thickness of less than 500 ⁇ m also has a lower mass inertia than membranes with a greater thickness. This is advantageous because when the sensor is accelerated, only small forces are exerted on the measuring arrangement by the inertial mass of the diaphragm, and acceleration therefore has little or no influence on a pressure measurement.
  • the metallic material is particularly preferably a fine-grained steel with a structure of martensite, bainite, needle ferrite, Widmann Toon ferrite or a mixture of these structures. These are generally not considered to be hydrogen resistant, but surprisingly they have reason due to its relatively fine-grained structure, it has a low tendency towards hydrogen embrittlement. Fine grain size leads to longer diffusion paths, which is why hydrogen cannot diffuse through these materials over a short distance. The metallic material therefore has a certain resistance to hydrogen. Bainite, needle ferrite and Widmann Toon ferrite are also known as intermediate structures. Intermediate structures include structures between martensite and pearlite. Needle ferrite is understood to mean the materials referred to in English as acicular ferrites.
  • the structures made of martensite, bainite, Widmann Toon ferrite, needle ferrite or a mixture of these structures are characterized by an average grain diameter of less than 20 ⁇ m and are therefore particularly suitable for the production of thin-walled membranes with thicknesses of less than 500 ⁇ m . Due to the small average grain diameter, the component has isotropic physical properties, which is advantageous when using the membrane.
  • the structure particularly preferably has a martensite with partially coherent or incoherent precipitations, preferably at grain boundaries within the material, as described in Metallischen, E. Hornbogen and H. Warlimont, 4th edition, Springer Verlag 2001. On. Partially coherent or incoherent precipitations in the sense of this description are in Materials Science - Steel - Volume 1, ventierir Eisenblinnleute (editor), Springer Verlag 1984 or in Pirlog, Madalina, and PK Pranzas. "CHARACTERIZATION OF COPPER PRECIPITATES IN FE-CU ALLOYS WITH SMALL-ANGLE NEUTRON SCATTERING". [0032] Incoherent and partially coherent precipitations act as hydrogen sinks.
  • Hydrogen accumulates at hydrogen sinks. This prevents the accumulated hydrogen from penetrating further into the material.
  • the mobility of the hydrogen is reduced compared to a material with coherent precipitations, since coherent precipitations are located within a grain, but hydrogen is preferably mobile along grain boundaries in the material.
  • the coating is part of the membrane.
  • the metallic material of the membrane has the coating.
  • the coating is arranged on the side of the metallic material of the membrane that faces the fluid medium.
  • the membrane has a coating.
  • the task of the coating is to reduce the permeability of the membrane with regard to atomic or molecular components of the fluid medium, in particular molecular and/or atomic hydrogen.
  • the coating is arranged between the metallic material of the membrane and the fluid medium, at least in the area which is in contact with the fluid medium during use.
  • the coating has oxides, carbides or nitrides.
  • Oxides, carbides or nitrides are, for example, aluminum oxides, aluminum carbides, aluminum nitrides, chromium oxides, chromium nitrides, silicon oxides, silicon carbides, silicon nitrides, titanium oxides, titanium carbides, titanium nitrides, zirconium oxides, or rare earth oxides.
  • the coating prevents direct contact between the metallic material of the diaphragm and the fluid medium. A direct adsorption of molecular and / or atomic components of the fluid medium on the metallic material Membrane is prevented by the coating.
  • the coating of the metallic material reduces a chemical reaction or dissociation of components on the surface of the coated material - dead membrane.
  • the corrosion resistance of the membrane is further increased compared to a membrane without a coating.
  • the coating is thinner than the thickness of the metallic material.
  • the thickness of the coating is preferably at most 10% of the total thickness of the membrane. Usual layer thicknesses are between 1 ⁇ m and 5 ⁇ m. The rigidity and yield point of the membrane is thus mainly determined by the metallic material.
  • the metallic material has a coefficient of thermal expansion between 5*10 -6 K -1 and 15*10 -6 K -1 in the temperature range between 20°C and 100°C.
  • epitaxial effects compensate for mismatches between the metallic material and the coating.
  • the adhesion of the coating to the metallic material is promoted by epitaxial effects if the layer is applied using epitaxial methods.
  • the coating also has a thermal expansion coefficient.
  • the coefficient of thermal expansion of the coating preferably deviates by no more than 50% from the coefficient of thermal expansion of the metallic material. This prevents delamination and cracking of the coating under thermal stress.
  • a thermal stress or change in temperature is when the temperature of at least a portion of the membrane increases or decreases by more than 10°C relative to a temperature at any previous time. The period of time is arbitrary and can be up to days.
  • the membrane has an adhesion promoter layer.
  • the task of the adhesion promoter layer is to prevent delamination of the coating from the metallic material. Mechanical stresses that occur when the temperature changes are thus advantageously distributed over an interface between the metallic material and the layer of adhesion promoter and a further interface between the layer of adhesion promoter and the coating. As a result, local mechanical stresses are lower and crack formation under mechanical or thermal stress is prevented.
  • the adhesion promoter layer is advantageously a metal with a high oxygen affinity, for example a refractory metal, aluminum or rare earth metals.
  • Refractory metals are titanium, vanadium, chromium, zirconium, niobium, hafnium, tantalum, molybdenum or tungsten.
  • the adhesion promoter layer has a purity of at least 75% by weight. A purity of at least 75% by weight means that 75% by weight of the adhesion promoter layer consists of a metal.
  • the adhesion promoter layer preferably consists of at least 90% by weight of zirconium or tungsten. zirconium or
  • Tungsten can easily be applied as a layer.
  • Membrane a coating of a non-stoichiometric oxide or a non-stoichiometric nitride or a non-stoichiometric carbide.
  • An oxide or a nitride or a carbide is non-stoichiometric if the chemical elements are not present in the optimum ratio for the respective mixture.
  • the optimal ratio is usually the most stable chemical compound.
  • Examples of stoichiometric carbides are SiC (silicon carbide), Al4C3 (aluminum carbide) or TiC (titanium carbide).
  • the constant x M,C depends on the element M for carbides C.
  • the x M,C is stoichiometric Ratio for the respective element M in connection with carbon C achieved. Other elements for M can also be used.
  • the stoichiometric ratio of the carbide can be determined in the technical literature.
  • Examples of stoichiometric nitrides are AlN (aluminum nitride), CrN (chromium nitride), Si 3 N 4 (silicon nitride), TiN (titanium nitride).
  • the constant x M,N depends on the element M for nitrides N.
  • At x M,N is the stoichiometric ratio for the respective element M in connection with nitrogen reached N. Other elements for M can also be used.
  • the stoichiometric ratio of the nitride can be determined in the technical literature.
  • a stoichiometric oxide is, for example, Al 2 O 3 (aluminum oxide), SiO 2 (silicon oxide), TiO 2 (titanium oxide), ZrO 2 (zirconium oxide), Cr 2 O 3 (chromium oxide), or, in the case of a rare earth oxide SC 2 O 3 , Y 2 O 3 , La 2 O 3 , CeO 2 , Pr 2 O 3 , Nd 2 O 3 , Pm 2 O 3 , Sm 2 O 3 , EuO, Gd 2 O 3 , Tb 2 O 3 , Dy2O3 , Ho2O3 , Er2O3 , Tm2O3 , Yb2O3 , LU2O3 .
  • a rare earth oxide SC 2 O 3 , Y 2 O 3 , La 2 O 3 , CeO 2 , Pr 2 O 3 , Nd 2 O 3 , Pm 2 O 3 , Sm 2 O 3 , EuO, Gd 2 O 3 , Tb 2
  • Rare earths are Sc (scandium), Y (yttrium), La (lanthanum), Ce (cerium), Pr (praseodymium), Nd (neodymium), Pm (promethium), Sm (samarium), Eu ( Europium), Gd (Gadolinium), Tb (Terbium), Dy (Dysprosium), Ho (Holmium), Er (Erbium), Tm (Thulium), Yb (Ytterbium), Lu (Lutetium).
  • the constant x M,0 depends on the element M for oxides 0. At x M,0 the stoichiometric ratio for the respective element M in connection with oxygen 0 is reached. Other elements for M can also be used. The stoichiometric ratio of the oxide can be determined for other elements M in the specialist literature.
  • the coating of a non-stoichiometric oxide or a non-stoichiometric nitride or a non-stoichiometric carbide is advantageous since the coefficient of thermal expansion of non-stoichiometric oxides, nitrides or carbides can be adjusted.
  • the coefficient of thermal expansion of the coating preferably does not deviate by more than 50% of the thermal expansion coefficient of the metallic material. This prevents delamination and cracking in the coating under thermal stress.
  • An adhesion promoter layer can be omitted in this embodiment.
  • a coating which has a carbide can also have a nitride.
  • So-called carbonitrides are expressly disclosed both in a coating containing carbides and in a coating containing nitrides. Examples are mixtures of titanium carbide and titanium nitride (titanium carbonitride), zirconium carbide and zirconium nitride (zirconium carbonitride), or chromium carbide and chromium nitride (chromium carbonitride).
  • the oxides, nitrides and carbides given by way of example have a Vickers hardness above 100 HV.
  • the coating of the metallic material therefore has increased mechanical resistance compared to a gold coating known from the prior art.
  • Vickers hardness is understood to mean the Vickers hardness with a test force of 10 kiloponds or 10 kgf (kilogram force), the so-called HV 10.
  • the Vickers hardness test is described in the DIN EN ISO 6507-1:2018 to -4:2018 standard.
  • the coating preferably has non-stoichiometric aluminum oxides or non-stoichiometric titanium carbides.
  • Aluminum oxide is known in the industry as a chemically inert material. In addition, aluminum oxide comparatively cheap compared to rare earths or zirconium. Titanium carbides are also widely used industrially and are known as a cheap, largely chemically inert material.
  • gold which is also largely chemically inert and has a Vickers hardness of less than 100 HV 10
  • aluminum oxide has a Vickers hardness of more than 1500 HV 10 and therefore, as a coating on a metallic material, has increased mechanical resistance compared to a gold coating.
  • Titanium carbide has a Vickers hardness of over 2500 HV 10 and as a coating on a metal material it therefore has increased mechanical resistance compared to a gold coating.
  • the coefficient of thermal expansion of the coating preferably deviates from the coefficient of thermal expansion of the metallic material by no more than 50%. This prevents delamination and cracking in the coating under thermal stress.
  • An adhesion promoter layer can be omitted in this embodiment.
  • the constants x M,C , X M,N , x M,0 depend on the element M for carbides C, nitrides N and oxides 0 and correspond to the stoichiometric ratio for the respective element M in conjunction with Carbon C, nitrogen N or oxygen 0.
  • the proportion y increases gradually within the coating with increasing distance from the metallic material.
  • the proportion x within the coating increases gradually as the distance from the metallic material increases.
  • the proportion x and the proportion y within the coating can also gradually increase as the distance from the metallic material increases. This has the advantage that the coating at the interface between the coating and the metallic material can be specifically adapted to the metallic material by selecting the proportions x and y.
  • An adjustment can minimize stresses at the interface and/or be an adjusted coefficient of thermal expansion.
  • the gradient within the coating is advantageous because physical properties change gradually within the coating as well. Tensions or cracks in the coating are avoided in this way.
  • the properties can be matched to the fluid medium.
  • the coating can also be exposed to other substances in the fluid medium in addition to hydrogen, and through the selection of the proportions x and y can have a higher resistance to other substances, for example gases or liquids containing caustic or acid.
  • the coefficient of thermal expansion of the coating made of non-stoichiometric oxide (1-y)M-yMO x , non-stoichiometric nitride (1-y)M-yMN x , or non-stoichiometric carbide (1-y)M-yMC x with gradients within the coating at the interface between metallic material and coating by no more than 50% from the thermal expansion coefficient of the metallic material.
  • the coating of non-stoichiometric aluminum oxide (1-y)Al-yAlO x particularly preferably has a gradient within the coating.
  • the proportion y increases gradually within the coating with increasing distance from the metallic material.
  • the proportion x within the coating increases gradually as the distance from the metallic material increases.
  • the proportion x and the proportion y within the coating can also gradually increase as the distance from the metallic material increases.
  • the coefficient of thermal expansion of the coating at the interface between the metallic material and the coating does not deviate by more than 50% from the coefficient of thermal expansion of the metallic material.
  • the membrane has at least one further coating.
  • the further coating is arranged on the side of the coating facing away from the metallic material.
  • the further coating has stoichiometric oxide or stoichiometric carbide or stoichiometric nitride on.
  • the coefficient of thermal expansion of the coating is advantageously between the coefficient of thermal expansion of the metallic material and the coefficient of thermal expansion of the additional coating.
  • the coating partially takes on the task of the adhesion promoter layer, but retains its task of reducing the permeability of the membrane with regard to molecular and/or atomic hydrogen. The permeability of the membrane with respect to molecular and/or atomic hydrogen is further reduced by the additional coating.
  • stoichiometric oxide or stoichiometric nitride or stoichiometric carbide has increased chemical resistance compared to non-stoichiometric oxide or non-stoichiometric nitride or non-stoichiometric carbide; they are particularly chemically inert.
  • the gradient within the coating is advantageous since physical properties change gradually within the coating as well. Tensions or cracks in the coating are avoided in this way.
  • the components x and y can be selected in such a way that stresses, even under thermal stress, are minimal.
  • the additional coating has a stoichiometric composition that is particularly chemically inert.
  • an adhesion promoter layer as already described, can be provided between the coating and the metallic material.
  • the coating goes at a distance of the interface between the coating and the metallic material into a stoichiometric oxide, nitride or carbide.
  • the membrane with a coating of non-stoichiometric oxide, nitride or carbide with a gradient, the coating goes into the respective stoichiometric oxide, nitride or carbide at a distance from the interface between the coating and the metallic material carbide over.
  • a further stoichiometric coating is applied to a non-stoichiometric coating.
  • the coefficient of thermal expansion of the coating is then advantageously between the coefficient of thermal expansion of the metallic material and the coefficient of thermal expansion of the further coating.
  • the membrane has at least one further coating, with a first further coating being arranged on the side of the coating facing the fluid medium and each additional further coating being arranged on the side of the previous further coating facing the fluid medium coating.
  • the at least one further coating has a non-stoichiometric carbide, nitride or oxide, analogously to the coating already described.
  • the further coating has a different chemical composition than the coating. If, for example, the coating is a titanium oxide, titanium nitride or titanium carbide, the further coating can be an aluminum nitride, aluminum oxide or aluminum carbide.
  • the chemical composition is corresponding different from adjacent further coatings. This has the advantage that the further coating in contact with the fluid medium can be adapted to the fluid medium, for example to resistance to other substances contained in the fluid medium.
  • the coating can also be matched to the metallic material.
  • the membrane has at least one further coating.
  • the further coating is arranged on the side of the coating facing away from the metallic material.
  • the additional, further coating has stoichiometric aluminum oxide Al 2 O 3 .
  • the coefficient of thermal expansion of the coating lies between the coefficient of thermal expansion of the metallic material and the coefficient of thermal expansion of the further coating.
  • the coating partially takes on the task of the adhesion promoter layer, but retains its task of reducing the permeability of the membrane with regard to molecular and/or atomic hydrogen. The permeability of the membrane with respect to molecular and/or atomic hydrogen is further reduced by the additional coating.
  • the membrane has an inner coating to reduce the permeability with regard to molecular and/or atomic hydrogen.
  • the inner coating is arranged on the side of the metallic material of the membrane facing away from the fluid medium in the second space.
  • the inner coating has a non-stoichiometric oxide or nitride or carbide.
  • the same oxides, carbides or nitrides that have already been described with regard to the coating are advantageous.
  • the application can thus take place at the same time as the coating.
  • the inner coating is particularly advantageous when the second space, which the membrane separates from the first space containing the fluid medium, is a closed volume.
  • a closed volume can be, for example, the interior of a housing of a transducer.
  • the additional inner coating further reduces the diffusion of molecular or atomic hydrogen through the membrane, as a result of which less hydrogen is enriched in the second space. If a pressure transmission medium is arranged in the closed volume, the negative effects described above, such as inflation of the membrane, are avoided.
  • inner coating and coating do not have identical chemical compositions. Since the coating is in contact with the fluid medium but not the inner coating, different coatings can be selected. For example, the inner coating or coating can be designed to be electrically insulating. Also can the coating has a resistance to other substances that the inner coating does not have to have.
  • an adhesion promoter layer can also optionally be arranged between the inner coating and the metallic material of the membrane.
  • the invention also includes a sensor for determining a pressure of a fluid medium.
  • the sensor has a pressure-side end facing the fluid medium.
  • the pickup has a housing.
  • the pickup has a measuring arrangement.
  • the measuring arrangement is arranged inside the housing.
  • the sensor has a membrane in one of the embodiments described above.
  • the second space corresponds to a volume inside the housing.
  • a measuring arrangement for determining a pressure of a fluid medium is, for example, at least one piezoelectric crystal, which generates piezoelectric charges as a function of a pressure applied to the membrane.
  • the piezoelectric crystal is arranged in a preload sleeve which applies a preload to the piezoelectric crystal. Both negative and positive pressure changes can be detected.
  • a measuring arrangement can also contain capacitive measuring elements, which detect mechanical deformation as a change in capacitance.
  • a measuring arrangement can also have piezoresistive measuring elements or strain gauges, also referred to as strain gauges or DMS, which detect mechanical deformation as a change in electrical resistance. record status.
  • strain gauges also referred to as strain gauges or DMS.
  • DMS piezoresistive measuring elements
  • the person skilled in the art is familiar with further measuring arrangements which are used in sensors for determining a pressure of a fluid medium.
  • the membrane is arranged on the pressure-side end of the housing and hermetically separates the measuring arrangement from the fluid medium.
  • the housing and the membrane are connected with a material connection.
  • a material connection is, for example, a welded connection or a soldered connection.
  • a material connection with an adhesive is also conceivable.
  • the membrane has a first region which, in use, is in contact with the fluid medium.
  • the membrane has a second region which, in use, is not in contact with the fluid medium.
  • the material connection is arranged in the second area. Cohesive connections made as soldered or welded connections usually have a higher number of cracks or pores. Even in the case of a material connection using adhesive, the adhesive can be damaged by the fluid medium. The material connection is therefore advantageously arranged in the second area, which is not exposed to the fluid medium.
  • the membrane has a coating, this is arranged at least in the entire first area, but can also extend at least partially over the second area.
  • a second area is not in contact with the fluid medium within the meaning of this description if the concentration of corrosive components of the fluid medium in the second area corresponds to a maximum of 1% of the concentration of corrosive components in the first area.
  • the first and second areas can be separated from one another, for example, by a sealing element.
  • a metal seal such as a copper seal, a seal made of steel 1.4404 or 1.4301, a sealing element made of a metal alloy or metal-plated seals made of a metal alloy can be used.
  • Plastic seals are also known for certain temperature ranges and pressure ranges, for example made of polytetrafluoroethylene, fluoroelastomers or nitrile compounds. Other materials can also be considered as sealing elements.
  • the transducer is preferably used to determine a pressure of a fluid medium when the fluid medium is corrosive and conventional transducers cannot be used.
  • the sensor is particularly preferably used to determine a pressure of a fluid medium which has at least a proportion of molecular and/or atomic hydrogen.
  • hydrogen leads to so-called hydrogen embrittlement in a large number of metallic materials, which leads to hydrogen embrittlement and a reduction in the yield strength under thermal and/or mechanical stress.
  • a pickup as described above greatly reduces these disadvantages.
  • All of the described embodiments of a receiver are specified as an embodiment with a second space. ordered pressure transmission medium possible. However, all of the described embodiments can also be executed without a pressure transmission medium arranged in the second space.
  • the invention also includes a sensor for determining a temperature of a fluid medium.
  • the sensor has a pressure-side end facing the fluid medium.
  • the pickup has a housing.
  • the sensor has a measuring arrangement for determining a temperature of a fluid medium.
  • the measuring arrangement is arranged inside the housing.
  • the sensor has a membrane in one of the embodiments described above.
  • FIG. 1 shows a schematic sectional view of an embodiment of a sensor with an embodiment of a membrane according to the invention, with an optional coating being represented by the dot-dash line;
  • FIG. 2 shows a schematic sectional view of an embodiment of a membrane
  • FIG. 3 shows a schematic sectional view of a further embodiment of a membrane
  • FIG. 4 shows a schematic sectional view of a further embodiment of a membrane
  • Fig. 5 shows a schematic sectional view of part of a transducer with a membrane according to Fig. 3, which is arranged in a wall;
  • Fig. 6 shows a schematic sectional view of part of a transducer with a membrane according to Fig. 2, which is arranged in a wall;
  • FIG. 7 shows a schematic sectional view of a further embodiment of a membrane
  • FIG. 8 shows a schematic sectional view of a further embodiment of a membrane
  • FIG. 9 shows a schematic sectional view of a further embodiment of a membrane.
  • FIG. 1 shows a schematic sectional view of an embodiment of a sensor 1 with an embodiment of a membrane 2 according to the invention, with an optional coating 4 being represented by the dot-dash line.
  • FIGS. 2 to 6 show the coating of a membrane 2 in the following, which differs from the illustration in FIG. 1.
  • FIGS. 2 to 9 show further embodiments of a membrane 2.
  • the thickness of the membrane 2 and the thickness of the coating 4 are not shown proportionally in each case for better clarification.
  • 5 to 6 show further embodiments of a sensor 1 with a membrane 2.
  • the thickness of the membrane 2 and the thickness of the coating 4 are not shown proportionally for better clarity.
  • the membrane 2 of FIGS. 1 to 6 comprises a metallic material 3 and hermetically separates a first space 14 from a second space 15 .
  • a fluid medium 13 of which at least one physical variable can be determined.
  • a physical variable is, for example, a pressure and/or a temperature.
  • the surface 6 of the membrane 2 faces the fluid medium 13 .
  • the membrane 2 has a first region 9 which is in contact with the fluid medium 13 when the membrane 2 is used.
  • the membrane 2 has a second region 10 which, in use, is not in contact with the fluid medium 13, as shown in FIGS. 1 to 6.
  • the membrane 2 advantageously has a thin-walled area 21 .
  • the thin-walled area 21 preferably has a thickness of less than 500 ⁇ m in order to transmit a pressure of a fluid medium 13 from the first space 14 to a second space 15 with as little loss as possible.
  • the membrane 2 in the embodiments of FIGS. 1 to 6 has the coating 4 to reduce the permeability with respect to molecular or atomic hydrogen.
  • which coating 4 is arranged between the metallic material 3 of the membrane 2 and the fluid medium 13 at least in the area which is in contact with the fluid medium 13 when in use.
  • the coating is shown as an option in the form of a dot-dash line.
  • the membrane 2 has an adhesion-promoting layer 5 which prevents the coating 4 from delaminating from the metallic material 3 of the membrane 2 .
  • the membrane 2 has a further coating 4 ′, which is arranged on the side of the coating 4 facing away from the metallic material 3 .
  • the membrane 2 has at least one further coating 4′, 4′′, 4′′′′, .
  • the further coating 4', 4'', 4''',... has a non-stoichiometric carbide, nitride or oxide, analogous to the coating 4 already described.
  • the membrane 2 has, for example, an inner coating 22 in addition to a coating 4 on the side of the metallic material 3 facing the fluid medium 13 .
  • the inner coating 22 is arranged on the side of the metallic material 3 of the membrane 2 facing away from the fluid medium 13 in the second space 15 .
  • an inner coating 22 is also possible, even if not shown in the figures.
  • the membrane 2 has a coating 4 and an adhesion promoter layer 5 on the side of the metallic material 3 of the membrane 2 that faces the fluid medium 13 .
  • this embodiment of the membrane 2 has on the side of the metallic material 3 facing away from the fluid medium 13 an adhesion promoter layer 5 which connects an inner coating 22 to the metallic material 3 .
  • FIG. 1 and 5 to 6 each show an embodiment of a membrane 2 in a sensor 1 for determining a pressure of a fluid medium 13.
  • the sensor 1 has a pressure side facing the fluid medium 13 - sat end 11 on.
  • the pickup 1 has a housing 7 .
  • a measuring arrangement 16 is arranged in the housing 7 .
  • FIG. 1, FIG. 5 or FIG. 6 shows a membrane 2 according to the invention.
  • the membrane 2 is arranged on the pressure-side end 11 of the sensor 1 and hermetically separates the measuring arrangement 16 from the fluid medium 13.
  • the housing 7 and membrane 2 are connected by a material connection 8.
  • the membrane 2 has a first region 9 which is in contact with the fluid medium 13 when in use.
  • the membrane 2 has a second region 10 which is not in contact with the fluid medium 13 when in use.
  • the first and second areas 9 , 10 are separated from one another by a sealing element 12 when the sensor 1 is used.
  • the materially bonded connection 8 is arranged in the second region 10 in each of the illustrated embodiments. However, it is also conceivable to arrange the material connection 8 in an area 9,10 which is in contact with the fluid medium 13 when the membrane 2 is used.
  • the integral connection 8 is advantageously completely covered with the coating 4 .
  • FIGS. 5 and 6 show the sensor 1 inserted into a wall 17 for use in determining a pressure of a fluid medium 13 .
  • the wall 17 can be, for example, a wall 17 of a tank for a fluid medium 13, a compressor, a heat pump, a refrigerator, a line for a fluid medium 13, a combustion chamber of an internal combustion engine or a gas turbine.

Landscapes

  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Measuring Fluid Pressure (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

L'invention concerne une membrane (2) permettant de séparer hermétiquement une première chambre (14) comprenant un milieu fluide contenant de l'hydrogène (13) d'une seconde chambre (15) ; la membrane (2) comportant un matériau métallique (3) ; la membrane (2) comportant un revêtement (4) destiné à réduire la perméabilité à l'hydrogène moléculaire et/ou atomique, ce revêtement (4) étant situé entre le matériau métallique (3) de la membrane (2) et le milieu fluide (13), au moins dans une zone qui, lors de l'utilisation, est en contact avec le milieu fluide (13) ; le revêtement (4) comportant au moins un oxyde, un carbure ou un nitrure non stœchiométrique.
PCT/EP2022/081288 2021-12-23 2022-11-09 Membrane pour utilisation avec des milieux contenant de l'hydrogène, et transducteur comprenant une telle membrane WO2023117198A1 (fr)

Applications Claiming Priority (2)

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EP21217511 2021-12-23
EP21217511.1 2021-12-23

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WO2023117198A1 true WO2023117198A1 (fr) 2023-06-29

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Country Link
US (1) US20230204446A1 (fr)
EP (1) EP4202392A1 (fr)
JP (1) JP2023094564A (fr)
KR (1) KR20230096867A (fr)
CN (1) CN116337313A (fr)
WO (1) WO2023117198A1 (fr)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10132691A (ja) * 1996-10-31 1998-05-22 Hitachi Ltd ダイアフラム
US20050109114A1 (en) 2003-11-20 2005-05-26 Wilson Ronald W. Cylinder pressure transducer and related method
JP2011185758A (ja) * 2010-03-09 2011-09-22 Yokogawa Electric Corp 圧力測定器
DE102014118616A1 (de) * 2014-12-15 2016-06-16 Endress + Hauser Gmbh + Co. Kg Druckmessaufnehmer

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Publication number Priority date Publication date Assignee Title
JP4185478B2 (ja) * 2004-07-23 2008-11-26 長野計器株式会社 歪検出器およびその製造方法
DE102014104113A1 (de) * 2014-03-25 2015-10-01 Kavlico GmbH Drucksensor für Wasserstoffanwendungen
JP6797649B2 (ja) * 2016-11-29 2020-12-09 セイコーインスツル株式会社 ダイヤフラムの製造方法

Patent Citations (4)

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Publication number Priority date Publication date Assignee Title
JPH10132691A (ja) * 1996-10-31 1998-05-22 Hitachi Ltd ダイアフラム
US20050109114A1 (en) 2003-11-20 2005-05-26 Wilson Ronald W. Cylinder pressure transducer and related method
JP2011185758A (ja) * 2010-03-09 2011-09-22 Yokogawa Electric Corp 圧力測定器
DE102014118616A1 (de) * 2014-12-15 2016-06-16 Endress + Hauser Gmbh + Co. Kg Druckmessaufnehmer

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
RAMANAVICIUS SIMONAS ET AL: "Insights in the Application of Stoichiometric and Non-Stoichiometric Titanium Oxides for the Design of Sensors for the Determination of Gases and VOCs (TiO2-x and TinO2n-1 vs. TiO2)", SENSORS, vol. 20, no. 23, 1 December 2020 (2020-12-01), CH, pages 6833, XP093025523, ISSN: 1424-8220, DOI: 10.3390/s20236833 *

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US20230204446A1 (en) 2023-06-29
CN116337313A (zh) 2023-06-27
KR20230096867A (ko) 2023-06-30
JP2023094564A (ja) 2023-07-05
EP4202392A1 (fr) 2023-06-28

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